Cyclic hydrocarbon and process for preparing the same



Patented Sept 30, 1930 7 UNITED, STATES PATENT OFFICE om'ro NIG'ODEMUS AND WALTER BERNDT, or HoonsT-oN-THE-MAm, GERMANY, As-

- 'bon atom which is in B position to the car bon atom marked G containsahydrogen -used as starting materials in SIGNOBS T0 GENERAL ANILINE WORKS,

TION or DELAWARE INC NEW YORK, N. Y., A CORPORA- cYoLIo' HYDROGARBONANDPROCESS FORPREPVARING THE SAME v no Drawing. Original applicatiozrfiled April 20, was, Serial No. 103,357fand in Germany June 22, 1925.

Divided and this application filed November 21, 1927. Serial- Ne 234,906.

The present invention relates to a process of preparing cyclic compounds and to new products obtainable thereby. Itssubject matter has been divided outfrom-our application Serial No. 103,357, filed April 20, 1-926.

Wehave found that when the vapors of certain compounds are conducted at an eleh vated temperature overghighly porous bodies,

such as highly active charcoal, silicagel or aluminagel; newcyclic systems are formed with a good yield a'ndin acontinuous and technically rapid way. The compoundsto be our process possess the atom grouping:

longing to an aromatic" or heterocyclic nucleus, X represents an aliphatic, aromatic or heterocychc residue, in WlllChfll? least one caratomattached to it and Y represents hydrogen, chlorine'orahydrocarbonresidue. t

I The term elevated temperature? in our specification is intendedto comprise such rem peratures as are sulficient to cause a ring closing but are below a carbonizing temperature.

It will be obvious that the suitable-temperature ranges can be easily determined-byexperiment. The'temperature ranges generally preferred by uS vary between about 320 C.

and about 450 C; a A V We have found that all secondary and tertiary aromatic or mixed alcohols, containing a methyl or methylenegroup in orthoposition to the carbinol group arefcapable of forming cyclic chains; In this connection it has been observedthat secondary reactions which are caused by the reducing action of the hydrogen produced during the operation are advantageously avoided by conducting the alcohol vapours, mixed with oxygene'efor instance with airor with oxygen-yielding the alcohol group is free which renders V ble the formation of the cyclic chain.

agents, such as nitro bodies,over the highly porous bodiesto which, if desired, some further oxygen carrying catalysts niay'be added for instance: a

The closing of the chain takes place in this case with simultaneous formation of 2 mol.

ester. group in form ofalcohol or an acid,

p'rovided, of course, that an-ortho-position to possizThe following examples serve to illustrate our invention and their wide range of appli- I (1') Over a contact-substance consisting of highly active charcoal (activated with phos tact furnace the reaction product iscondensed in 'a receiver and then separatedfroni the "wa- *phoric acid) and charged with copper-cobalter Which has formed and recrystallized from toluene. Thus there is obtained L t-7- 'trimethylanthracene M. P. 226 CQ in the amount of 50% of the theory. The unaltered 7 starting material, after thelsolveut has been distilled therefrom, is returned into the, furnace. following equations HOE; s f

(2) Ortho toluyl-5-acenaphthene is rea duced' and the carbinol,=which melts at 145 one dissolves in sulfuric acid with an indigesblue tint; is "distilled mixed With air The reaction occurs according to the under reduced pressure over a catalyst made of highly active charcoal and heated to 320-340 C. Having regard to the fact that the acenaphthene derivative is highly decomposable, care must be taken that the passage of the gas through the reaction zone takes place rapidly. The product of the reaction is obtained as a solid cake which is dissolved hot in ligroine of a high boiling point. On cooling, the anthracene of the acenaphthene separates as light yellow leaflets which melt at 191 C. and dissolve in sulfuric acid with a reddish violet color of a strong fluorescence. The closing of the ring occurs according to the following scheme:

CHflCH2 CHz-CH:

HO. \O

The yield amounts to of the theory. The unaltered parent material is returned into the contact furnace. Analysis Of the above mentioned anthracene showed:

94.17% C. 5.78% H. against 94.4% C. 6.6% H.

(3) Over a catalyst, consisting of highly active charcoal heated to 400 C. are conducted the vapours of m-xylenecarbinolacetate mixed with air during which operation the ester eiiects the closing of the ring to form the B-methylanthracene with elimination of acetic acid and water. By recrystallizing the reaction product from glacial acetic acid the fi'methylanthracene is obtained in a pure state and with a yield-of 30%, the mother liquors containing benzoyliii-xylene in the amount of of the ester employed.

e claim:

1. As a new product acenaphtanthracene of the following constitution:

as previously calculated.

l/l V melting at 191 C. forming yellow laminae which are soluble in concentrated sulfuric acid with a reddish violet colour and an intense fluorescence.

v 2. lhe process which comprises conducting over highly porous bodies having highly active properties and the property of extensively absorbing gases and vapors, at a temperature sufficient to cause a ring closing but below a carbonizing temperature, the vapors of a compound possessing the atom groupingz H OH wherein G and C represent carbon atoms belonging to an aromatic or heterocyclic nucleus, X represents an aliphatic, aromatic or heterocyclic residue, in which at least one carbon atom which is in ,B-position to the carbon atom marked C contains a hydrogen atom attached to it and Y represents hydrogen, chlorine or a hydrocarbon residue.

3. The process which comprises conducting over highly porous bodies, having highly active properties and the property of extensively absorbing gases and vapors, at temperatures between 320 C. and 450 C. in the presence of an oxygen carrying catalyst the vapors of a compound possessing the atom grouping wherein C and C represent carbon atoms belonging to an aromatic or heterocyclic nucleus, X represents an aliphatic, aromatic or heterocyclic residue, in which at least one carbon atom which is in ,8-position to the carbon atom marked C contains ahydrogen atom attached to it, and Y represents hydrogen, chlorine or a hydrocarbonresidue.

4. The process which comprises conducting over highly porous bodies, having highly active properties and the property of extensively absorbing gases and vapors, at temperatures between 320 C. and 450 C. in the presence of an oxygen carrying catalyst and oxidizing media the vapors of a compound possessing the atom grouping H on;

A; Y A041; \11 wherein C and C represent carbon atoms belonging to an aromatic or heterocyclic nucleus, X represents an aliphatic, aromatic or heterocychc resldue, 1n Whlch at least one carbon atom which is in B-position to the carbon atom marked C contains a hydrogen atom attached to it, and Y represents hydrogen, chlorine or a hydrocarbon residue. 7

5. As new products cyclic compounds which are produced by closing the ring of compounds of the formula Y r (-11 \H wherein the symbols signify the following 1' R an acenaphthene orv heterocyclic substi tuted or nonsubstituted. residue; IY hydro;

gen or chlorine or a hydrocarbon residue; X an aliphatic, aromatic or heterocyclic residue, in which at least one carbon atom which is in ,B-position to the atom marked G contains a hydrogen atom attached to it.

In testimony whereof we aflix our signatures. 7

DR. OTTO NICODEMUS. DR. WALTER BERNDT. 

